US2009281126A1PendingUtilityA1

Organic Compounds

Assignee: NOVARTIS AGPriority: Apr 21, 2006Filed: Apr 19, 2007Published: Nov 12, 2009
Est. expiryApr 21, 2026(expired)· nominal 20-yr term from priority
A61P 43/00A61P 29/00A61P 19/02C07D 473/40C07D 473/34C07D 403/08C07D 473/00A61K 31/52
47
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Claims

Abstract

A compound of formula (I) and their preparation and use as pharmaceuticals wherein R 1 , R 2 and R 3 are as defined herein.

Claims

exact text as granted — not AI-modified
1 . A compound of formula I 
     
       
         
         
             
             
         
       
     
     in free or salt form, wherein
 R 1  denotes a N-bonded 3- to 12-membered heterocyclic group containing from 1 to 4 ring nitrogen atoms and optionally containing from 1 to 4 other heteroatoms selected from the group consisting of oxygen and sulfur, that group being optionally substituted by oxo, C 1 -C 8 -alkoxy, C 6 -C 10 -aryl, R 1a  or by C 1 -C 8 -alkyl optionally substituted by OH, or 
 R 1  is —NH—C 1 -C 8 -alkylcarbonyl, —NH—C 3 -C 8 -cycloalkylcarbonyl, —NH—SO 2 —C 1 -C 8 -alkyl, —NH—C 7 -C 14 -aralkylcarbonyl, —NH—C(═O)-3- to 12-membered heterocyclic group, —NH—C(═O)—C 6 -C 10 -aryl or —NH—C(═O)—C(═O)—NH—C 1 -C 8 -alkyl optionally substituted by R 1a , where R 1a  is a 3- to 12-membered heterocyclic group containing at least one ring heteroatom selected from the group consisting of nitrogen, oxygen and sulphur, said 3- to 12-membered heterocyclic ring being optionally substituted by halo, cyano, oxo, OH, carboxy, amino, nitro, C 1 -C 8 -alkyl, C 1 -C 8 -alkylsulfonyl, aminocarbonyl, C 1 -C 8 -alkylcarbonyl or C 1 -C 8 -alkoxy optionally substituted by aminocarbonyl; 
 R 2  is selected from the group consisting of C 1 -C 8 -alkyl, R— and S— 1-phenylethyl, an unsubstituted benzyl group, and a phenylethyl or benzyl group substituted in one or more positions with a substituent selected from the group consisting of C 1 -C 8 -alkyl, amino, halo, C 1 -C 8 -haloalkyl, nitro, OH, acetamido, C 1 -C 8 -alkoxy and sulfo, or 
 R 2  is 
 
     
       
         
         
             
             
         
       
       where
 R 2a  is halo, trifluoromethyl, cyano, C 1 -C 8 -alkyl, C 1 -C 8 -alkyloxy, ethenyl or ethynyl; 
 D is oxy, thio, NH, C 1 -C 8 -alkyloxy, C 1 -C 8 -alkylthio or —CO-alkylamino; and 
 G is a partially saturated, fully saturated or fully unsaturated 5- to 8-membered ring optionally having 1 to 3 heteroatoms selected independently from oxygen, sulfur and nitrogen, or, a bicyclic ring consisting of two fused partially saturated, fully saturated or fully unsaturated 3- to 6-membered rings, taken independently, optionally having 1 to 4 heteroatoms selected independently from nitrogen, sulfur and oxygen; wherein said G is optionally mono-, di- or tri-substituted independently with halo, C 1 -C 8 -alkyl, trifluoromethyl, trifluoromethoxy, nitro, cyano, C 3 -C 10 -cycloalkyl, hydroxy or C 1 -C 8 -alkoxy, or 
 G is cyano, C 1 -C 8 -alkoxycarbonyl, C 3 -C 10 -cycloalkoxycarbonyl, C(O)NR 4 R 5 , C(S)NR 4 R 5 , C(NH)NR 4 NR 5 , C(N(C 1 -C 3 )alkyl)NR 4 R 5  or C(N(C 3 -C 10 )cycloalkyl)NR 4 R 5 ; 
 R 3  is selected from H, halo, C 1 -C 8 -alkyl optionally substituted by halo or OH, C 1 -C 8 -alkoxy, amino, C 1 -C 8 -alkylamino, C 2 -C 10 -alkenes, C 2 -C 10 -alkynes optionally substituted by C 1 -C 8 -alkyl, aryl optionally substituted by C 1 -C 8 -alkyl or OH, thio and C 1 -C 8 -alkylthio; 
 R 4  is a bond, H, C 1 -C 10 -alkyl, hydroxy, C 1 -C 10 -alkoxy, C 3 -C 10 -cycloalkoxy or a partially saturated, fully saturated or fully unsaturated 5- to 8-membered ring, optionally linked through C 1 -C 8 -alkyl, optionally having 1 to 3 heteroatoms selected independently from oxygen, sulfur and nitrogen, or, a bicyclic ring or a bicyclic ring with optional C 1 -C 8 -bridge optionally linked through C 1 -C 8 -alkyl, said bicyclic ring or bridged bicyclic ring optionally having 1 to 4 heteroatoms selected independently from nitrogen, sulfur and oxygen wherein said C 1 -C 10 -alkyl, C 1 -C 10 -alkoxy, C 3 -C 10 -cycloalkoxy or R 4  ring(s) is optionally mono-, di- or tri-substituted independently with halo, C 1 -C 8 -alkyl, trifluoromethyl, nitro, cyano, C 3 -C 10 -cycloalkyl, OH or C 1 -C 8 -alkoxy; 
 R 5  is a bond, H, C 1 -C 8 -alkyl or C 1 -C 10 -cycloalkyl, and 
 R 4  and R 5 , taken together with the nitrogen to which they are attached, form a fully saturated or partially unsaturated four to nine membered ring, said ring optionally bridged, optionally having 1 to 3 heteroatoms selected independently from oxygen, sulfur and nitrogen, said ring optionally mono- or di-substituted independently with oxo, hydroxy, C 1 -C 8 -alkoxy, C 1 -C 8 -alkyl, amino, mono-N— or di-N,N—C 1 -C 8 -alkylaminocarbonyl, mono-N— or di-N,N—C 3 -C 10 -cycloalkylaminocarbonyl, N—C 1 -C 8 -alkyl-N—C 3 -C 10 -cycloalkylaminocarbonyl, mono-N— or di-N,N—C 1 -C 8 -alkylamino, mono-N— or di-N,N—C 3 -C 10 -cycloalkylamin, N—C 1 -C 8 -alkyl-N—C 3 -C 10 -cycloalkylamino, formylamino, C 1 -C 8 -alkylcarbonylamino, C 3 -C 10 -cycloalkylcarbonylamino, C 1 -C 8 -alkoxycarbonylamino, N—C 1 -C 8 -alkoxycarbonyl-N—C 1 -C 8 -alkylamino, C 1 -C 8 -sulfamoyl, C 1 -C 8 -alkylsulfonylamino, C 3 -C 10 -cycloalkylsulfonylamino or a partially saturated, fully saturated or fully unsaturated 5- to 8-membered ring, optionally linked through C 1 -C 8 -alkyl, optionally having 1 to 3 heteroatoms selected independently from oxygen, sulfur and nitrogen, or, a bicyclic ring consisting of two fused partially saturated, fully saturated or fully unsaturated 3- to 6-membered rings, taken independently, optionally linked through C 1 -C 8 -alkyl, optionally having 1 to 4 heteroatoms selected independently from nitrogen, sulfur and oxygen, and optionally mono- or di-substituted with halo, trifluoromethyl, trifluoromethoxy, C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy. 
 
     
   
   
       2 . A compound according to  claim 1 , 
     wherein
 R 1  denotes a N-bonded 3- to 12-membered heterocyclic group containing from 1 to 4 ring nitrogen atoms and optionally containing from 1 to 4 other heteroatoms selected from the group consisting of oxygen and sulphur, or 
 R 1  is —NH—C 1 -C 8 -alkylcarbonyl; 
 R 2  is C 1 -C 8 -alkyl or benzyl optionally substituted by halogen, or 
 R 2  is 
 
     
       
         
         
             
             
         
       
       where
 R 2a  is halo, trifluoromethyl, cyano, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, ethenyl or ethynyl; 
 D is oxy, thio, NH, C 1 -C 8 -alkoxy, C 1 -C 8 -alkylthio or —CO-alkylamino; and 
 G is a partially saturated, fully saturated or fully unsaturated 5- to 8-membered ring optionally having 1 to 3 heteroatoms selected independently from oxygen, sulfur and nitrogen, or, a bicyclic ring consisting of two fused partially saturated, fully saturated or fully unsaturated 3- to 6-membered rings, taken independently, optionally having 1 to 4 heteroatoms selected independently from nitrogen, sulfur and oxygen; wherein said G is optionally mono-, di- or tri-substituted independently with halo, C 1 -C 8 -alkyl; and 
 
       R 3  is selected from H, halo, C 1 -C 8 -alkyl optionally substituted by halo or OH, C 1 -C 8 -alkoxy, amino, C 1 -C 8 -alkylamino, C 2 -C 10 -alkenes, C 2 -C 10 -alkynes optionally substituted by C 1 -C 8 -alkyl, C 6 -C 10 -aryl optionally substituted by C 1 -C 8 -alkyl or OH, thio and C 1 -C 8 -alkylthio. 
     
   
   
       3 . A compound according to  claim 1 , 
     wherein
 R 1  is a 5 to 12-membered heterocyclic group containing at least one ring heteroatom selected from the group consisting of nitrogen, oxygen and sulphur, or 
 R 1  is —NH—C 1 -C 8 -alkylcarbonyl; 
 R 2  is 
 
     
       
         
         
             
             
         
       
       where
 R 2a  is halogen; 
 D is C 1 -C 8 -alkoxy; and 
 G is a 5-membered heterocyclic group substituted by a methyl group, or 
 
       R 2  is a benzyl substituted by halogen, or 
       R 2  is C 1 -C 8 -alkyl; and 
       R 3  is H, halo or C 2 -C 10 -alkynes optionally substituted by C 1 -C 8 -alkyl. 
     
   
   
       4 . A compound of formula I, according to  claim 1   
     
       
         
         
             
             
         
       
       where R 1 , R 2  and R 3  are 
     
     
       
         
               
               
               
             
                   
               
                 R 1   
                 R 2   
                 R 3   
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 Cl 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 Cl 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 CH 3   
                 
                   
                     
                     
                         
                         
                     
                   
                 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 
                   
                     
                     
                         
                         
                     
                   
                 
                 H 
               
                   
               
           
              
              
              
             
             
              
              
              
              
              
              
              
              
              
              
             
          
         
       
     
   
   
       5 . A compound according to  claim 1  for use as a pharmaceutical. 
   
   
       6 . Pharmaceutical compositions comprising a compound according to  claim 1 . 
   
   
       7 . The use of a compound according to  claim 1 , in the manufacture of a medicament for the treatment of a condition mediated by activation of the adenosine A 3  receptor. 
   
   
       8 . The use of a compound according to  claim 7 , wherein said condition mediated by activation of the adenosine A 3  receptor is rheumatoid arthritis. 
   
   
       9 . A process for the preparation of compounds of formula (I) 
     
       
         
         
             
             
         
       
       where R 1 , R 2  and R 3  are as defined hereinbefore, which comprises the steps of: 
       (i) (A) for the preparation of compounds of formula (I), reacting a compound of formula (Ia) 
     
     
       
         
         
             
             
         
       
       
         where R 2  and R 3  are as hereinbefore defined, with acetyl chloride in the presence of base; 
         (B) for the preparation of compounds of formula (I), where R 3  is C 2 -C 8 -alkynyl, reacting a compound of formula (Ib) 
       
     
     
       
         
         
             
             
         
       
       
         where X is a leaving group, with a compound of formula 
       
     
     
       
         
         
             
             
         
       
     
     where R can be C 1 -C 6 -alkyl;
   (C) for the preparation of compounds of formula (I), reacting a compound of formula (Ic)   
 
     
       
         
         
             
             
         
       
       
         where
 R 1  and R 3  are as hereinbefore defined; and 
 X is a leaving group, with a compound of formula H 2 N—R 2 , where R 2  is as hereinbefore defined in the presence of a base; and 
 
       
       (ii) recovering the resultant compound of formula (I), in free or pharmaceutically acceptable salt form.

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